Bitumen and aggregate composition and a building block molded therefrom



BITUMEN AND AGGREGATE COMPOSITION AND A BUILDING BLOCK MOLDED THEREFROMDuane W. Gagle and Charles E. Defabaugh, Bartlesville,

Okla., assignors to Phillips Petroleum Company, a corporation ofDelaware No Drawing. Original application August 18, 1952, Serial No.305,068, now Patent No. 2,775,530, dated December 25, 1956. Divided andthis application February 10, 1956, Serial No. 564,645

8 Claims. (Cl. 106-280) This invention relates to improvements inmixtures of asphalt and aggregate. In a more specific aspect thisinvention relates to improved paving compositions comprising bitumen andaggregate compositions which are resistant to deterioration by water. Inanother specific aspect it relates to improved asphalt-aggregate pavingcompositions.

This application is a division of our copending application Serial No.305,068, filed August 18, 1952, now U.S. Patent No. 2,775,530.

Paving compositions are widely used which are composed of mineralaggregate and bituminous constituents, usually asphalt. This type ofpavement while economical and durable has a disadvantage of beingsubject to deterioration by moisture. Many mineral aggregates have agreater afiinity for water than for asphalt; there fore, manyasphalt-coated aggregate compositions such as are used in surfacingroads and streets are adversely affected by moisture. Even when theaggregate is already coated with asphalt, water in vapor or liquid formwill slowly permeate the asphalt to the surface of the aggregate. Sincethe aggregate is hydrophilic it becomes coated with a water film whichtends to loosen and strip the asphalt from the aggregate.

The following objects will be attained by the aspects of this invention.

It is an object of this invention to provide a bituminousmaterial-mineral aggregate composition which is resistant to moisture.

It is another object to provide a paving composition which is resistantto decomposition by moisture.

It is another object to provide a method for preserving bitumen-mineralaggregate paving composition.

It is another object to provide a bitumen composition having anincreased afiinity for mineral aggregate.

It is still another object to provide a method for preventing thestripping of asphalt from rock aggregate by the action of moisture.

Other objects will be apparent to one skilled in the art upon readingthis disclosure.

We have found that the adhesion of asphalt, or road oil to aggregate inthe presence of water may be very substantially improved by use ofcertain additives in an asphalt-aggregate mixture. Our improvedcomposition comprises a road oil or asphalt, aggregate, a heavy,unsaturated oil, obtained as a by product in an HF catalyzed process,and an inorganic metal compound such as aluminum sulfate or lime(calcium hydroxide). The road oil, inorganic metal compound, andunsaturated oil may be mixed together and the aggregate subsequentlycoated with the resulting composition. Alternatively, the aggregate maybe coated with the inorganic metal compounds in the form of a solutionor slurry in water or as a dry powder, and subsequently coated with theroad oil containing the acid-soluble oil. The additives may also beemployed in an emulsified asphalt with equal success. Other polyvalentinorganic metal compounds including lead nitrate, ferrous nitrate,ferric nitrate, barium hydroxide, zinc sulfate, ferrous chloride-ferricchloride, calcium oxide, copper sulfate, etc., can be used, however,lime and aluminum sulfate are preferred.

5 2,889,231 Ratented June 2, 1959 ice In hydrocarbon conversionprocesses in which hydrofiuoric acid is employed as a catalyst, forexample, alkyla tion and isomerization reactions, a hydrocarbon phaseand an acid phase are formed. The hydrocarbon phase and acid phase areseparated and hydrofluoric acid is, recovered from the acid phase and isreturned to the conversion system. The materials remaining after theremoval of the hydrofluoric acid from the acid phase comprise acomposition known as HR acid-soluble oil. It is not known :as to exactlywhat materials make up the acid-soluble oil. The acid-soluble oil is,however, highly unsaturated, high in aromatic content, and uponevaporation of the more volatile fractions leaves a solid resin.

In the case of a typical commercial process for the alkylation ofisoparaflins with olefins, the charge to the alkylation reactorcomprises an isoparaflin stream, for example, a stream which ispredominantly isobutane, and an olefin stream containing, for example,butylenes, with or without other olefins such as propylene and amylenes.Normal paraflins and alkyl cycloparafiins can be similarly alkylatedwith an olefin. The primary product is an alkylate suitable for use inmaking aviation gasoline. In the case of aromatic alkylation the chargeto the reactor may contain benzene, toluene or other aromatic hydro}carbon, and an olefin the exact nature of which depends upon the productdesired. Thus, if long chain alkyl aromatics are being produced forsubsequent sulfonation to form synthetic detergents, the olefin streammay comprise C to C mono olefins. In either case, however, the charge tothe HF alkylation process is substantially free from diolefiniccompounds. The formation of acidsoluble oils seems to be acharacteristic of all hydrocarbon conversions in which HP is employed asa catalyst, whether the primary reaction be one of alkylation,isomerization or olefin polymerization. Hence the chemical nature of theacid-soluble oil is quite different from that of the diolefin polymerformed in the clay treating and sulfuric acid treating processes, whichare well known in the art.

We have discovered that the heavier fraction of such an HF acid-solubleoil, that is, the fraction boiling above 250 F. is a particularlyeffective anti-strip agentin road oils or asphalts when used with arnetal compound in the manner previously described. These oils have anAPI gravity between 14 and 24, an iodine No.(Wijs) above 150, preferableabove 170, a Saybolt Universal viscosity at 210 F. between 40 and 150secs., 3. pour point above 10 F., a non-volatile fraction between 50 andpercent according to ASTM D154-50, and are highly aromatic in character.

The amount of additive oil to be used depends upon the character of thebitumen and the aggregate, but from 0.1 to 3 weight percent of theweight of bitumen is generally satisfactory. The amount of inorganicmetal compound varies from .2 to 5 times the weight of acid soluble oilemployed.

EXAMPLE I In the following tests a typical HF acid-soluble. oil, ob.-tained by the HF alkylation of isobutane with butylenes, was employedwhich had the following characteristics;

Gravity, API l7.1 SUV at 210 F. Flash, COC F 265 Iodine 9- l--,--r,----- 1 8 Percent non-volatile 83.3 Acid No. 0.46 Free acid 0.004Percent F 0-.154 Percent S 0.072

Preparation of the aggregate Passing /4 inch 100 Passing 4 mesh 60.0Passing mesh 32.4 Passing 40 mesh 14.4 Passing 200 mesh 9.6

Strip tests In these tests the additives were added to the road oil inthe percentages noted, based on road oil plus additive, in Table I. Ineach case the aggregate was oiled by hand at 60 C. with 3.5 percent ofthe road oil-additive mix. The oiled samples (200 grams each) wereallowed to stand in air for 24 hours at room temperature, then wereimmersed in 400 cc. of tap water in a quart glass jar and soaked 24hours after which time they were mechanically shaken in a Ro-tap(commercial laboratory screen shaking machine) for a period of minutes.After removal from the Ro-tap, the fines were decanted onto a 200 Mscreen, and the stripped fines washed through. Ten cc. of 0.05 M AlClwere added to the washings to induce flocculation, the water decantedfrom the settled fines, and the fines dried in an oven at 80 C. Theseparated and dried fines were then weighed to determine the weight ofstripped fines (through 200' mesh).

The road oil used in this test was a straight run SC-3 asphalt.

The condition of the coarse aggregate was visually observed and isreported qualitatively as good, fair, or poor.

metal compound to bitumen aggregate paving compositions.

We claim:

1. A moisture resistant paving composition comprising bitumen; mineralaggregate; from 0.02 to 15 weight percent of said bitumen of analkali-earth metal hydroxide; and from 0.1 to 3 weight percent of saidbitumen of HF acid-soluble oil obtained as a by-product from an HFcatalyzed hydrocarbon conversion process and having a higher boilingpoint than any of the reactant hydrocarbons.

2. The composition of claim 1 wherein the HF acidsoluble oil is obtainedby the HF alkylation of paraifins with olefins.

3. The composition of claim 1 wherein the HF acidsoluble oil has an APIgravity between 14 and 24; an iodine number above 150; a viscosity at210 F. between 40 and 150 seconds; a pour point above 10 F.; and anon-volatile fraction between and 85 percent.

4. A composition comprising bitumen; mineral aggre gate; from 0.02 to 15weight percent of said bitumen of calcium hydroxide; and from 0.1 to 3weight percent of said bitumen of HF acid-soluble oil obtained as abyproduct from an HP catalyzed hydrocarbon conversion process and havinga higher boiling point than any of the reactant hydrocarbons.

5. A composition comprising bitumen; mineral aggregate; from 0.02 to 15weight percent of said bitumen of barium hydroxide; and from 0.1 to 3weight percent of said bitumen of HF acid-soluble oil obtained as a by-'product from an HP catalyzed hydrocarbon conversion process and having ahigher boiling point than any of the reactant hydrocarbons.

6. A building block molded from a composition comprising emulsifiedasphalt; mineral aggregate; from 0.1 to 3 weight percent of said asphaltof HF acid-soluble oil obtained as a by-product in the HF catalyzedconversion TABLE I Test N0 1 2 3 4 5 6 7 8 Acid-Soluble Oil, wt. Percent0 14. 3 0 1 0 1 0 1 Inorganic Metal Compound Pb(N0a)2 PMNOa): lime limeAMSO-Ds AMSOi); Weight Percent 1 1 1 l l 1 Percent Strip (Fines) 40. 5754. 62 45. 38.30 38. 3 13. 6 8. 39 2. 95 Strip (Coarse) Poor Poor PoorFair Fair Fair Fair Good The acid-soluble oil when used as asingleadditive, does not appear to improve the stripping qualities ofthe aggregate tested. When the acid-soluble oil is used in conjunctionwith a metal compound, for example, aluminum sulfate, lead nitrate, or alime a marked improvement in the stripping qualities of the aggregate isshown.

The synergistic efiect of acid-soluble oil upon the composition ofasphalt-aggregate paving materials constitutes a valuable forward stepin the preparation of lasting and economical road building materials.

The compositions of this invention are also particularly suitable formaking construction units or building blocks suitable for moderate sizedbuildings. These building blocks are usually made in forms or moulds andare 12 inches by 18 inches by 4 inches in size. Emulsified asphalt isusually employed and when the blocks have dried or cured they aremortared together with fresh bitumen-aggregate composition. Smalleraggregate are ordinarily used in building blocks than are used in pavingcompositions.

Building blocks made with the compositions of this invention areresistant to moisture and can be painted with oil base paints. H

Reasonable variations and modifications are possible within the scope ofthe disclosure to the present invention, the essence of which is thatimproved paving compositions having resistance to deterioration bymoisture are made possible. by incorporation of HF acid-soluble oils anda of hydrocarbons and having a boiling point above 250 F.; and from 0.02to 15 weight percent of said asphalt of an alkali-earth metal hydroxide.

7. A composition comprising bitumen; an alkali-earth metal hydroxide;and an HF acid-soluble oil obtained as a by-product from an HP catalyzedhydrocarbon conversion process and having a higher boiling point thanany of the reactant hydrocarbons, said hydroxide and said acidsolubleoil being present in amounts sufiicient to increase the afiinity of thebitumen for mineral aggregate.

8. A composition comprising bitumen; up to 15 weight percent of saidbitumen of an alkali-earth metal hydroxide; and up to 3 weight percentof said bitumen of an HF acid-soluble oil obtained as a by-product froman HE catalyzed hydrocarbon conversion process and having a higherboiling point than any other reactant hydrocarbon, said hydroxide andsaid acid-soluble oil being present in an amount sufficient to increasethe atfinity of the bitumen for mineral aggregate.

References Cited in the file of this patent UNITED STATES PATENTS Gagleet al Dec. .25, 1956

1. A MOISTURE RESISTANT PAVING COMPOSITIION COMPRISING BITUMEN; MINERAL AGGREGATE; FROM 0.02 TO 15 WEIGHT PERCENT OF SAID BITUMENT OF AN ALKALI-EARTH METAL HYDROXIDE; AND FROM 0.1 TO 3 WEIGHT PERCENT OF SAID BITUMENT OF HF ACID-SOLUBLE OIL OBTAINED AS A BY-PRODUCT FROM AN HF CATALYZED HYDROCARBON CONVERSION PROCESS AND HAVING A HIGHER BOILING POINT THAN ANY OF THE REACTANT HYDROCARBONS. 